Method for producing 1-indanoles and 1-indanamines

ABSTRACT

A description is given of a process for preparing 1-indanols and 1-indanamines by palladium-catalyzed arylation and of the use thereof as intermediates for the synthesis of fine chemicals and of active agrochemical ingredients.

The invention relates to a process for preparing 1-indanols and1-indanamines by palladium-catalyzed arylation and to the use thereof asintermediates for the synthesis of fine chemicals and of activeagrochemical ingredients.

1-Indanols and 1-indanamines of the formula (I), in which Y is asubstituted hydroxyl or amino group, constitute an important structuralelement in a multitude of agronomically active substances, as disclosed,for example, in WO 2004/069814 A1 and WO 2007/112834 A1.

J. A. Pincock et al.: “The Photochemistry of Conformationally RigidBenzylic Esters: 2,2-Dimethyl-1-indanyl Acetates and Pivalates”, TheJournal of Organic Chemistry 1995, 13, 4067, describe the preparation of1-indanols by reduction of the corresponding 1-indanones.

Hui Fang et al.: “Rapid Catalyst Screening by a Continuous-FlowMicroreactor Interfaced with Ultra-High-Pressure Liquid Chromatography”,The Journal of Organic Chemistry 2010, 16, 5619, describe the synthesisof an indanamine starting from the corresponding3-(3,4-dimethoxyphenyl)-2,2-dimethylpropanenitrile or from an acylaminalprecursor.

From C. Pierre, O. Baudoin, Org. Lett. 2011 13, 1816 and N. Martin, C.Pierre, M. Davi, R. Jazzar, O. Baudoin, O. Chem.-Eur. J. 2012, 18, 4480,palladium(0)-catalyzed arylations of 2-haloketones (IIa) or 2-halocompounds (IIb) are known. The starting compounds (IIa) and (IIb) are inboth cases compounds in which there is a carbon atom in the 2-positionrelative to the halogen atom on the phenyl ring that does not carry ahydrogen atom (C═O in formula IIa and CRY, with R and Y each being otherthan hydrogen, in formula IIb):

However, the processes specified in these documents for preparing1-indanols and 1-indanamines are restricted to performance on thelaboratory scale, since they have a number of disadvantages and are thusunusable for industrial production. A further very significantdisadvantage of the known prior art processes via palladium-catalyzedarylation of 2-halo compounds is the fact that they have so far beendescribed solely for starting compounds (IIa) and (IIb) in which thereis a carbon atom in the 2-position relative to the halogen atom on thephenyl ring that does not carry a hydrogen atom, and so lead toformation of 1-indanols and 1-indanamines (Ia) in which R is nothydrogen.

For preparing the abovementioned agronomically active substances,however, it is the 1-indanols and 1-indanamines of the formula (I) thatare of interest as intermediates, i.e., those in which the carbon atomsubstituted by the radical Y still carries a hydrogen atom.

It is an object of the present invention to provide a process forpreparing 1-indanols and 1-indanamines which overcomes the disadvantagesof the processes known from the prior art.

It has now been found that 1-indanols and 1-indanamines can be preparedin high yields by palladium-catalyzed arylation of1-(2-halophenyl)alkan-1-ols or 1-(2-halophenyl)alkan-1-amines.

The present invention accordingly provides a process for preparing1-indanols and 1-indanamines of the general formula (I) which comprisesreacting 1-(2-halophenyl)alkan-1-ols or 1-(2-halophenyl)alkan-1-amines(II) at elevated temperature under palladium catalysis in the presenceof phosphine ligands, a base, and a solvent,

and in which the radicals, symbols, and indices are defined as follows:

-   -   Y is NR¹R² or OR³,    -   R¹ is hydrogen or COR⁴,    -   R² is COR⁴,    -   or R¹ and R² together form the group COCH₂CH₂CO or        CO-phenylene-CO,    -   R³ is Si(R⁵)₃ or pivaloyl (2,2-dimethylpropanoyl),    -   R⁴ is (C₁-C₆)-alkyl or phenyl,    -   R⁵ is (C₁-C₆)-alkyl or phenyl,    -   Hal is chlorine, bromine or iodine,    -   R is fluorine, (C₁-C₃)-alkyl or (C₁-C₃)-alkoxy,    -   X¹ is hydrogen or (C₁-C₆)-alkyl,    -   X² is hydrogen or (C₁-C₆)-alkyl,    -   X³ is hydrogen or (C₁-C₆)-alkyl,    -   X⁴ is hydrogen or (C₁-C₆)-alkyl,        or    -   X¹ and X², or    -   X³ and X⁴, or    -   X¹ and X³ together with the carbon atom to which they are bonded        form in each case a 3- to 7-membered saturated ring,        or    -   Y and X¹ together with the carbon atoms to which they are bonded        form a 5- to 7-membered saturated ring,    -   m is 0, 1, 2 or 3.

Suitable palladium catalysts are, for example, Pd(OAc)2, Pd2dba3(tris(dibenzylideneacetone)dipalladium(0)), PdCl2, and PdBr2, withPd(OAc)2 being preferred. The palladium catalyst is used customarily inan amount of 0.1 to 10 mol %, preferably 1 to 10 mol %, more preferably1 to 5 mol %, based on the compound (II).

Suitable phosphine ligands are, for example, trialkylphosphines,tricycloalkylphosphines such as tricyclohexylphosphine,triarylphosphines such as triphenylphosphine, tri-ortho-tolylphosphine,tri(4-dimethylaminophenyl)phosphines, and alkyldiarylphosphines such asbutyldiphenylphosphine, with triphenylphosphine being particularlypreferred. The phosphines may also be used in the form of salts, withHBF4, for example, The phosphine ligands are used customarily in anamount of 0.1 to 10 mol %, preferably 1 to 10 mol %, more preferably 1to 5 mol %, based on the compound (II).

Palladium catalysts and phosphine ligands can be used as separatecompounds or usefully in the form of a preformed complex—for example, astetrakis(triphenylphosphinyl)palladium, which is particularly preferred.

Suitable bases are, for example, carbonates, hydrogencarbonates,phosphates, alkoxides, and carboxylates of alkali metals, such asLi₂CO₃, Na₂CO₃, K₂CO₃, NaHCO₃, KHCO₃, K₃PO₄, K₂HPO₄, NaOMe, NaOEt,NaOiPr, NaOtBu, KOMe, KOEt, KOiPr, KOtBu, NaOAc, KOAc, NaOPiv (sodiumpivalate), KOPiv. NaOCOPh, and KOCOPh or mixtures of such bases.Mixtures of carbonates and carboxylates are preferred. The mixture ofK₂CO₃ and KOPiv is particularly preferred. The base is used customarilyin a 1- to 5-molar proportion, based on the compound (II).

Suitable solvents are, for example, aromatics such as toluene, xylene,chlorobenzene, and anisole; ethers such as dibutyl ether, diphenylether, and polyglycol ethers; esters such as butyl acetate and isopropylacetate; amides such as dimethylacetamide, dimethylformamide, anddibutylformamide, or mixtures thereof. Particularly preferred arearomatic solvents such as xylene.

The preparation process of the invention is carried out customarily atelevated temperature of more than 100° C. up to the boiling point of thesolvent in question. A range from 120 to 150° C. is preferred, Shouldthe boiling point of the solvent in question be below this, it is usefulto work under superatmospheric pressure.

The process is carried out preferably for compounds of the formulaespecified above in which the radicals, symbols, and indices are definedas follows:

-   -   Y is NR¹R² or OR³,    -   R¹ is hydrogen or COR⁴,    -   R² is COR⁴,    -   R³ is Si(R⁵)₃ or 2,2-dimethylpropanoyl,    -   R⁴ is tert-butyl,    -   R⁵ is isopropyl,    -   Hal is bromine or iodine,    -   R is fluorine, methyl or methoxy,    -   X¹ is hydrogen or methyl,    -   X² is hydrogen or methyl,    -   X³ is hydrogen or methyl,    -   X⁴ is hydrogen or methyl,        or    -   X¹ and X², or    -   X³ and X⁴, or    -   X¹ and X³ together with the carbon atom to which they are bonded        form in each case a 3- to 7-membered saturated ring,        or    -   Y and X¹ together with the carbon atoms to which they are bonded        form a 5- to 7-membered saturated ring,    -   m is 0, 1, 2 or 3.

In the formula (I) and all the formulae which follow, alkyl radicalshaving more than two carbon atoms may be straight-chain or branched.Alkyl radicals are, for example, methyl, ethyl, n- or isopropyl, n-,iso-, tert- or 2-butyl, pentyls, and hexyls, such as n-hexyl, isohexyl,and 1,3-dimethylbutyl.

The examples which follow illustrate the invention.

The abbreviations used here are:

Ac acetate Cy cyclohexyl Cyp cyclopentyl Me methyl Ph phenyl Pivpivalate TiPs triisopropylsilyl

General instructions:

Under inert gas, the palladium catalyst (0.015 mmol, 5 mol %),optionally the phosphine ligand (0.03 mmol, 10 mol %), and the base,e.g., potassium pivalate (0.030 mmol, 10 mol %) and K₂CO₃ (0.3 mmol, 1.0eq) are introduced and the solvent (3 ml of xylene) and a compound ofthe formula (II) (0.3 mmol, 1.0 eq) are added. The mixture is thenstirred at room temperature for 10 minutes and subsequently heated to140° C. and stirred at this temperature for 16 hours. After the reactionmixture has cooled to room temperature it is filtered, the solvent isstripped off, and the residue is purified by chromatography.

EXAMPLE 1 Preparation of2,2-dimethyl-2,3-dihydro-1H-inden-1-yl)oxy)triisopropylsilane from[1-(2-bromophenyl)-2,2-dimethylpropoxy](triisopropyl)silane

The reaction took place in line with the general instructions, with 5mol % of Pd(PPh₃)₄, and gave a yield of 89%.

¹H NMR (300 MHz, CDCl₃, 293 K) δ 1.01 (s, 3H), 1.06-1.25 (m, 24H), 2.60(d, J=15.2 Hz, 1H), 2.75 (d, J=15.2 Hz, 1H), 4.93 (s, 1H), 7.11-7.22 (m,3H), 7.29-7.38 (m, 1H).

EXAMPLE 2 Preparation of((2′,3′-dihydrospiro[cyclopropane-1,1′-inden]-3′-yl)oxy)triisopropylsilanefrom [1-(2-bromophenyl)-cyclopropylethoxy](triisopropyl)silane

The reaction took place in line with the general instructions, with 5mol % of Pd(PPh₃)₄, and gave a yield of 69%.

¹H NMR (300 MHz, CDCl₃, 293 K) δ 0.70-0.82 (m, 1H), 0.85-0.96 (m, 1H),1.00-1.27 (m, 23H), 2.31 (d, J=7.2 Hz, 2H), 5.60 (t, J=7.2 Hz, 1H),6.67-6.76 (m, 1H), 7.17-7.27 (m, 2H), 7.39-7.46 (m, 1H).

EXAMPLE 3 Preparation of((5,6-dimethoxy-2,2-dimethyl-2,3-dihydro-1H-inden-1-yl)oxy)triisopropylsilanefrom[1-(2-bromo-4,5-dimethoxyphenyl)-2,2-dimethylpropoxy](tri-tert-butypsilane

The reaction took place in line with the general instructions, with 5mol % of Pd(PPh₃)₄, and gave a yield of 84%.

¹H NMR (300 MHz, CDCl₃, 293 K) δ 1.02 (s, 3H), 1.06-1.25 (m, 24H), 2.53(d, J=15.0 Hz, 1H), 2.69 (d, J=15.0 Hz, 1H), 3.85 (s, 6H), 4.86 (s, 1H),6.69 (s, 1H), 6.89 (s, 1H).

EXAMPLE 4 Preparation of((6-methoxy-2,2-dimethyl-2,3-dihydro-1H-inden-1-yl)oxy)triisopropylsilanefrom[1-(2-bromo-5-methoxyphenyl)-2,2-dimethylpropoxy](tri-tert-butyl)silane

The reaction took place in line with the general instructions, with 5mol % of Pd(PPh₃)₄, and gave a yield of 81%.

¹H NMR (300 MHz, CDCl₃, 293 K) δ 0.98 (s, 3H), 1.05-1.28 (m, 24H), 2.54(d, J=14.8 Hz, 1H), 2.65 (d, J=14.8 Hz, 1H), 3.79 (s, 3H), 4.90 (s, 1H),6.73 (dd, J=2.5, 8.1 Hz, 1H), 6.89 (d, J=2.5 Hz, 1H), 7.04 (d, J=8.1 Hz,1H).

EXAMPLE 5 Preparation of((6-fluoro-2,2-dimethyl-2,3-dihydro-1H-inden-1-yl)oxy)triisopropylsilanefrom[1-(2-bromo-5-fluorophenyl)-2,2-dimethylpropoxy](tri-tert-butyl)silane

The reaction took place in line with the general instructions, with 5mol % of Pd(PPh₃)₄, and gave a yield of 84%.

¹H NMR (300 MHz, CDCl₃, 293 K) δ1.00 (s, 3H), 1.06-1.26 (m, 24H), 2.55(d, J=15.0 Hz, 1H), 2.68 (d, J=15.0 Hz, 1H), 4.90 (s, 1H), 6.87 (ddd,J=2.5, 81, 9.2 Hz, 1H), 7.00 (dd, J=2.5, 8.7 Hz, 1H), 7.07 (dd, J=5.2,8.1 Hz, 1H).

EXAMPLE 6 Preparation of 2,2-dimethyl-2,3-dihydro-1H-inden-1-yl2,2-dimethylpropanoate from 1-(2-bromophenyl)-2,2-dimethylpropyl2,2-dimethylpropanoate

The reaction took place in line with the general instructions, with 5mol % of Pd(PPh₃)₄, and gave a yield of 95%.

¹H NMR (300 MHz, CDCl₃, 293 K) δ 1.09 (s, 3H), 1.16 (s, 3H), 1.21 (s,9H), 2.69 (d, J=15.3 Hz, 1H), 2.87 (d, J=15.3 Hz, 1H), 5.81 (s, 1H),7.09-7.29 (m, 4H).

EXAMPLE 7 Preparation of6-methoxy-2,2-dimethyl-2,3-dihydro-1H-inden-1-yl 2,2-dimethylpropanoatefrom 1-(2-bromo-5-methoxyphenyl)-2,2-dimethylpropyl2,2-dimethylpropanoate

The reaction took place in line with the general instructions, with 5mol % of Pd(PPh₃)₄, and gave a yield of 88%.

¹H NMR (300 MHz, CDCl₃, 293 K) δ 1.09 (s, 3H), 1.16 (s, 3H), 1.22 (s,9H), 2.63 (d, J=15.3 Hz, 1H), 2.80 (d, J=15.3 Hz, 1H), 3.77 (s, 3H),5.79 (s, 1H), 6.77-6.84 (m, 2H), 7.05-7.12 (m, 1H).

EXAMPLE 8 Preparation of 6-fluoro-2,2-dimethyl-2,3-dihydro-1H-inden-1-yl2,2-dimethylpropanoate from1-(2-bromo-5-fluorophenyl)-2,2-dimethylpropyl 2,2-dimethylpropanoate

The reaction took place in line with the general instructions, with 5mol % of Pd(PPh₃)₄, and gave a yield of 76%.

¹H NMR (300 MHz, CDCl₃, 293 K) δ 1.08 (s, 3H), 1.16 (s, 3H), 1.22 (s,9H), 2.65 (d, J=15.4 Hz, 1H), 2.81 (d, J=15.4 Hz, 1H), 5.76 (s, 1H),6.87-6.99 (m, 2H), 7.08-7.15 (m, 1H).

EXAMPLE 9 Preparation of(3aR*,8bS*)-3a-methyl-3,3a,4,8b-tetrahydro-2H-indeno[1,2-b]furan-2-onefrom 5-(2-bromophenyl)-4,4-dimethyldihydrofuran-2(3H)-one

The reaction took place in line with the general instructions, with 5mol % of Pd(PPh₃)₄, and gave a yield of 88%.

¹H NMR (300 MHz, CDCl₃, 293 K) δ 1.34 (s, 3H), 2.45 (d, J=17.8 Hz, 1H),2.51 (d, J=17.8 Hz, 1H), 2.87 (d, J=16.4 Hz, 1H), 3.00 (d, J=16.4 Hz,1H), 5.32 (s, 1H), 7.13-7.29 (m, 3H), 7.36 (d, J=7.2 Hz, 1H).

EXAMPLE 10 Preparation of2-(2-methyl-2,3-dihydro-1H-inden-1-yl)isoindoline-1,3-dione from2-[1-(2-bromophenyl)-2-methylpropyl]-1H-isoindole-1,3(2H)-dione

The reaction took place in line with the general instructions, with 5mol % of Pd(PPh₃)₄, and gave a yield of 54% of the trans isomer.

¹H NMR (300 MHz, CDCl₃, 293 K) δ 1.27 (d, J=6.8 Hz, 3H), 2.65 (dd,J=8.6, 15.6 Hz, 1H), 3.00-3.18 (m, 1H), 3.37 (dd, J=8.2, 15.6 Hz, 1H),5.43 (d, J=8.2 Hz, 1H), 7.01 (d, J=7.6 Hz, 1H), 7.11-7.19 (m, 1H),7.20-7.30 (m, 2H), 7.70-7.79 (m, 2H), 7.82-7.91 (m, 2H).

EXAMPLE 11 Preparation of2-(2,2-dimethyl-2,3-dihydro-1H-inden-1-yl)isoindoline-1,3-dione from2-[1-(2-bromophenyl)-2,2-dimethylpropyl]-1H-isoindole-1,3(2H)-dione

The reaction took place in line with the general instructions, with 5mol % of Pd(PPh₃)₄, and gave a yield of 86%.

¹H NMR (300 MHz, CDCl₃, 293 K) δ 0.64 (s, 3H), 0.83 (s, 3H), 2.34 (d,J=15.6 Hz, 1H), 2.87 (d, J=15.6 Hz, 1H), 4.9 (s, 1H), 6.66-6.77 (m, 2H),6.80-6.89 (m, 2H), 7.16-7.33 (m, 3H), 7.42-7.49 (m, 1H).

EXAMPLE 12 Preparation of (1R,2S)-2,6-dimethylindan-1-amine from2-[1-(2-bromo-5-methylphenyl)-2-methylpropyl]-1H-isoindole-1,3(2H)-dionevia2-[(1R,2S)-2,6-dimethyl-2,3-dihydro-1H-inden-1-yl]-1H-isoindole-1,3(2H)-dione

The reaction took place initially in line with the general instructions,with 5 mol % of Pd(PPh₃)₄,

and gave a yield of 55% of the primary product.

¹H NMR (300 MHz, CDCl₃, 293 K) δ 1.24 (d, J=7.0 Hz, 3H), 2.25 (s, 3H),2.58 (dd, J=8.0, 15.7 Hz, 1H), 2.97-3.15 (m, 1H), 3.32 (dd, J=8.2, 15.7Hz, 1H), 5.37 (d, J=8.2 Hz, 1H), 6.80 (s, 1H), 7.03 (d, J=7.5 Hz, 1H),7.14 (d, J=7.5 Hz, 1H), 7.70-7.78 (m, 2H), 7.80-7.90 (m, 2H).

Then a solution of 0.17 mmol of2-(2,6-dimethyl-2,3-dihydro-1H-inden-1-yl)isoindoline-1,3-dione in 1 mlof methanol and 1 ml of THF was admixed at 0° C. with 1.7 mmol ofhydrazine hydrate. The mixture was then stirred at room temperature for12 hours. The mixture was filtered and concentrated, The residue waspartitioned between DCM and water, and the organic phase was isolatedand washed with saturated NaHCO₃. After drying over MgSO₄ andconcentration, the product was obtained as a solid with a yield of 98%.

¹H NMR (300 MHz, CDCl₃, 293 K) δ 1.25 (d, J=6.7 Hz, 3H), 1.68 (s, 2H),1.90-2.08 (m, 1H), 2.35 (s, 3H), 2.44 (dd, J=9.5, 15.3 Hz, 1H), 2.99(dd, J=7.7, 15.3 Hz, 1H), 3.76 (d, J=8.3 Hz, 1H) 7.01 (d, J=7.5 Hz, 1H),7.08 (d, J=7.5 Hz, 1H), 7.13 (s, 1H).

EXAMPLE 13 Preparation oftriisopropyl((2-methyl-2,3-dihydro-1H-inden-1-yl)oxy)silane from[1-(2-bromophenyl)-2-methylpropoxy](triisopropyl)silane

This reaction was executed with different palladium catalysts, phosphineligands, and quantities of bases. The results of these experiments,achieved under various conditions, are set out in table form:

Yield No. Pd cat. Phosphine K₂CO₃ KOPiv of theory 13a 5 mol % Pd(PPh₃)₄100 mol % 10 mol % 55% cis, 8% trans 13b 5 mol % Pd(OAc)₂ 10 mol % PCy₃110 mol % 10 mol % 47% cis, 5% trans 13c 5 mol % Pd(OAc)₂ 10 mol % PCyp₃110 mol % 10 mol % 41% cis, 5% trans 13d 5 mol % Pd(OAc)₂ 10 mol % PPh₃100 mol % 10 mol % 57% cis, 6% trans 13e 5 mol % Pd(OAc)₂ 10 mol % P(4-100 mol % 10 mol % 48% cis, 9% trans Me₂N—Ph)₃

cis isomer: ¹H NMR (300 MHz, CDCl₃, 293 K) δ 0.99 (d, J=6.9 Hz, 3H),1.08-1.25 (m, 21H), 2.56-2.68 (m, 2H), 2.92 (dd, J=7.1, 15.7 Hz, 1H),5.29 (d, J=5.8 Hz, 1H), 7.17-7.25 (m, 3H), 7.35-7.43 (m, 1H).

trans isomer: ¹H NMR (300 MHz, CDCl₃, 293 K) δ 1.05-1.31 (m, 24H),2.34-2.57 (m, 2H), 3.10-3.33 (m, 1H), 4.98 (d, J=5.0 Hz, 1H), 7.19-7.28(m, 3H), 7.37-7.46 (m, 1H).

1. A process for preparing a 1-indanol and/or a 1-indanamine of formula (I) which comprises reacting a 1-(2-halophenyl)alkan-1-ol or 1-(2-halophenyl)alkan-1-amine (II) at elevated temperature under palladium catalysis in the presence of one or more phosphine ligands, a base, and a solvent,

and in which the radicals, symbols, and indices are defined as follows: Y is NR¹R² or OR³, R¹ is hydrogen or COR⁴, R² is COR⁴, or R¹ and R² together form the group COCH₂CH₂CO or CO-phenylene-CO, R³ is Si(R⁵)₃ or 2,2-dimethylpropanoyl, R⁴ is (C₁-C₆)-alkyl or phenyl, R⁵ is (C₁-C₆)-alkyl or phenyl, Hal is chlorine, bromine or iodine, R is fluorine, (C₁-C₃)-alkyl or (C₁-C₃)-alkoxy, X¹ is hydrogen or (C₁-C₆)-alkyl, X² is hydrogen or (C₁-C₆)-alkyl, X³ is hydrogen or (C₁-C₆)-alkyl, X⁴ is hydrogen or (C₁-C₆)-alkyl, or X¹ and X², or X³ and X⁴, or X¹ and X³ together with the carbon atom to which they are bonded form in each case a 3- to 7-membered saturated ring, or Y and X¹ together with the carbon atoms to which they are bonded form a 5- to 7-membered saturated ring, m is 0, 1, 2 or
 3. 2. The process as claimed in claim 1, in which the radicals, symbols, and indices have the following definitions: Y is NR¹R² or OR³, R¹ is hydrogen or COR⁴, R² is COR⁴, R³ is Si(R⁵)₃ or 2,2-dimethylpropanoyl, R⁴ is tert-butyl, R⁵ isisopropyl, Hal is bromine or iodine, R is fluorine, methyl or methoxy, X¹ is hydrogen or methyl, X² is hydrogen or methyl, X³ is hydrogen or methyl, X⁴ is hydrogen or methyl, or X¹ and X², or X³ and X⁴, or X¹ and X³ together with the carbon atom to which they are bonded form in each case a 3- to 7-membered saturated ring, or Y and X¹ together with the carbon atoms to which they are bonded form a 5- to 7-membered saturated ring, m is 0, 1, 2 or
 3. 3. The process as claimed in claim 1 in which said palladium catalyst used is a compound from the group consisting of Pd(OAc)₂, tris(dibenzylideneacetone)dipalladium(0), PdCl₂, and PdBr₂.
 4. The process as claimed in claim 3, in which Pd(OAc)₂ is used.
 5. The process as claimed in any of claim 1, in which triphenylphosphine is used as ligand.
 6. The process as claimed in claim 1, in which tetrakis(triphenylphosphinyl)palladium is used as combined palladium catalyst and ligand.
 7. The process as claimed in claim 1, in which the palladium catalyst and the ligand or the combination thereof are/is used in each case in an amount of 0.1 to 10 mol %, based on the compound (II).
 8. The process as claimed in claim 7, in which the palladium catalyst and the ligand or the combination thereof are/is used in each case in an amount of 1 to 5 mol %, based on the compound (II).
 9. The process as claimed in claim 1, where said base used is a mixture of an alkali metal carbonate and an alkali metal pivalate.
 10. The process as claimed in claim 1, where the base is used in a 1- to 5-molar proportion, based on the compound (II).
 11. The process as claimed in claim 1, where said solvent used is from the group of the aromatics. 